铑催化的1,5-联烯-炔烃的Pauson-Khand型环化反应：一种用于光学活性双环酮的手性转移策略

Rhodium-Catalyzed Pauson-Khand-Type Cyclization of 1,5-Allene-Alkynes: A Chirality Transfer Strategy for Optically Active Bicyclic Ketones.

作者信息

Han Yulin, Zhao Yichuan, Ma Shengming

机构信息

State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai, 200032, P.R. China.

Research Center for Molecular Recognition and Synthesis, Department of Chemistry, Fudan University, 220 Handan Road, Shanghai, 200433, P.R. China.

出版信息

Chemistry. 2019 Jul 17;25(40):9529-9533. doi: 10.1002/chem.201900963. Epub 2019 Jun 17.

DOI:10.1002/chem.201900963

PMID:31033044

Abstract

An efficient chirality transfer in the [RhCl(CO) ] -catalyzed [2+2+1] cyclization of optically active axially chiral 1,3-disubstituted allenynes with CO to access optically active bicyclopentenone compounds has been developed. The distal C=C bond of allenes reacted with the alknye unit and CO to afford [4.3.0]-bicyclic products with high ee values under mild reaction conditions with an excellent selectivity.

摘要

已开发出一种在[RhCl(CO)]催化下，光学活性轴向手性1,3 - 二取代联烯炔与CO进行[2+2+1]环化反应以得到光学活性双环戊烯酮化合物的有效手性转移方法。在温和的反应条件下，联烯的远端C = C键与炔基单元和CO反应，以优异的选择性得到具有高对映体过量值（ee值）的[4.3.0] - 双环产物。